EP0324174B1 - Process for the preparation of 2-chloro-5-methylpyridine - Google Patents
Process for the preparation of 2-chloro-5-methylpyridine Download PDFInfo
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- EP0324174B1 EP0324174B1 EP88121826A EP88121826A EP0324174B1 EP 0324174 B1 EP0324174 B1 EP 0324174B1 EP 88121826 A EP88121826 A EP 88121826A EP 88121826 A EP88121826 A EP 88121826A EP 0324174 B1 EP0324174 B1 EP 0324174B1
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- European Patent Office
- Prior art keywords
- process according
- reaction
- methyl
- chloro
- pyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
Definitions
- the invention relates to a new process for the preparation of 2-chloro-5-methyl-pyridine.
- 2-chloro-5-methyl-pyridine can be obtained in addition to 2-chloro-3-methyl-pyridine, 4-chloro-3-methyl-pyridine and 3-chloro-5-methyl-pyridine if 3 -Methyl-pyridine-1-oxide is reacted with phosphoryl chloride (see Weissberger, Chemistry of Heterocyclic Compounds, Pyridine and its Derivatives, Vol. 14, Supplement, Part 2, p. 112).
- the main product of this reaction is 4-chloro-3-methyl-pyridine; the proportion of 2-chloro-5-methyl-pyridine is generally less than 25%.
- a new process for the preparation of 2-chloro-5-methyl-pyridine of the formula (I) has now been from 3-methyl-pyridine-1-oxide of the formula (II) and phosphoryl chloride, which is characterized in that the reaction is carried out in the presence of a basic organic nitrogen compound from the series dialkylamines, trialkylamines, dialkylcycloalkylamines, dialkylaralkylamines and dialkylarylamines and in the presence of an inert organic solvent at temperatures between -50 ° C. and +50 ° C. and work up the reaction product in the usual way.
- advantages of the process according to the invention are also that the proportion of isomeric by-products is significant is lower than in the previously known synthesis method.
- the pure compound (I) can easily be prepared from the reaction product by customary methods, for example by separation by distillation.
- the method according to the invention thus represents a valuable enrichment of the technology.
- the inventive method is in the presence of a basic nitrogen compound of the series dialkylamines, such as.
- a basic nitrogen compound of the series dialkylamines such as.
- diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine and di-sec-butylamine trialkylamines, such as. B. triethylamine, tripropylamine and tributylamine
- dialkyl-cycloalkylamines such as. B. dimethyl-cyclopentylamine, diethyl-cyclopentylamine, dimethyl-cyclohexylamine and dietyl-cyclohexylamine
- dialkyl-aralkylamines such as e.g. B. dimethyl-benzylamine and diethyl-benzylamine and dialkylarylamines, such as. B. Dimethylaniline performed.
- Diisopropylamine is particularly preferred as the basic organic nitrogen compound.
- the process according to the invention is carried out in the presence of an inert organic solvent.
- organic solvent preferably include optionally halogenated hydrocarbons, such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene, ether, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, diethyl ketone,
- Methylene chloride is particularly preferred as a diluent.
- reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between -50 ° C and +50 ° C, preferably at temperatures between -20 ° C and +20 ° C.
- the process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure between 0.1 and 10 bar.
- 1 mol of 3-methyl-pyridine-1-oxide of the formula (II) is generally employed between 1 and 10 mol, preferably between 1.5 and 2.5 mol, phosphoryl chloride and likewise between 1 and 10 Moles, preferably between 1.5 and 2.5 moles, of the basic organic nitrogen compound.
- the use of approximately 2 moles of phosphoryl chloride and nitrogen compound per mole of 3-methyl-pyridine-1-oxide is particularly preferred.
- the 3-methyl-pyridine-1-oxide is initially introduced into a diluent and, while stirring and cooling, the phosphoryl chloride dissolved in an inert organic solvent and the basic organic nitrogen compound likewise dissolved in an inert organic solvent are simultaneously (" simultaneously ",” in parallel "), preferably adding the phosphoryl chloride with a small time advantage, so that between 5% and 20% of the phosphoryl chloride is present in the reaction mixture when the addition of the basic organic nitrogen compound is started. The complete reaction mixture is stirred until the reaction has ended.
- the workup can be carried out in the usual way.
- Water is preferably added to the reaction mixture with stirring and cooling, the organic solvent is removed, for example by distillation, and the aqueous phase is dissolved in an aqueous alkali metal or alkaline earth metal hydroxide solution, such as, for. B. sodium hydroxide solution, adjusted to pH 6 and the reaction product largely removed by steam distillation.
- the organic portion of the steam distillate essentially contains the product of formula (I).
- the pure preparation of the compound of formula (I) from the organic portion of the steam distillate can be carried out by customary methods, for example by fine distillation on a packed column.
- the compound of formula (I) has a boiling point of 56 ° C. at a pressure of 3.3 mb.
- the overall yield in the production of pure product (I) starting from 3-methyl-pyridine-1-oxide is 55-62% of theory.
- the 2-chloro-5-methyl-pyridine which can be prepared by the process according to the invention is known as an intermediate for pharmaceuticals (cf. DE-OS 28 12 585).
- 2-chloro-5-methyl-pyridine can be used as an intermediate for active insecticides.
Description
Die Erfindung betrifft ein neues Verfahren zur Herstellung von 2-Chlor-5-methyl-pyridin.The invention relates to a new process for the preparation of 2-chloro-5-methyl-pyridine.
Es ist bekannt, daß man 2-Chlor-5-methyl-pyridin neben 2-Chlor-3-methyl-pyridin, 4-Chlor-3-methyl-pyridin und 3-Chlor-5-methyl-pyridin erhält, wenn man 3-Methyl-pyridin-1-oxid mit Phosphorylchlorid umsetzt (vgl. Weissberger, Chemistry of Heterocyclic Compounds, Pyridine and its Derivatives, Vol. 14, Supplement, Part 2, S. 112). Hauptprodukt dieser Umsetzung ist 4-Chlor-3-methyl-pyridin; der Anteil an 2-Chlor-5-methyl-pyridin liegt im allgemeinen unter 25 %.It is known that 2-chloro-5-methyl-pyridine can be obtained in addition to 2-chloro-3-methyl-pyridine, 4-chloro-3-methyl-pyridine and 3-chloro-5-methyl-pyridine if 3 -Methyl-pyridine-1-oxide is reacted with phosphoryl chloride (see Weissberger, Chemistry of Heterocyclic Compounds, Pyridine and its Derivatives, Vol. 14, Supplement, Part 2, p. 112). The main product of this reaction is 4-chloro-3-methyl-pyridine; the proportion of 2-chloro-5-methyl-pyridine is generally less than 25%.
Es wurde nun ein neues Verfahren zur Herstellung von 2-Chlor-5-methyl-pyridin der Formel (I)
aus 3-Methyl-pyridin-1-oxid der Formel (II)
und Phosphorylchlorid gefunden, welches dadurch gekennzeichnet ist, daß man die Umsetzung in Gegenwart einer basischen organischen Stickstoffverbindung der Reihe Dialkylamine, Trialkylamine, Dialkylcycloalkylamine, Dialkylaralkylamine und Dialkylarylamine und in Gegenwart eines inerten organischen Lösungsmittels bei Temperaturen zwischen -50 °C und +50 °C durchführt und das Reaktionsprodukt in üblicher Weise aufarbeitet.A new process for the preparation of 2-chloro-5-methyl-pyridine of the formula (I) has now been
from 3-methyl-pyridine-1-oxide of the formula (II)
and phosphoryl chloride, which is characterized in that the reaction is carried out in the presence of a basic organic nitrogen compound from the series dialkylamines, trialkylamines, dialkylcycloalkylamines, dialkylaralkylamines and dialkylarylamines and in the presence of an inert organic solvent at temperatures between -50 ° C. and +50 ° C. and work up the reaction product in the usual way.
Es ist als überraschend anzusehen, daß gemäß dem erfindungsgemäßen Verfahren unter Verwendung von basischen organischen Stickstoffverbindungen 2-Chlor-5-methylpyridin in erheblich höherer Ausbeute als nach der bisher bekannten Methodik erhalten werden kann, da bei Einsatz von Phosphoryl-chlorid und basischen organischen Stickstoffverbindungen nebeneinander eher mit Nebenprodukten aus der Reaktion dieser Komponenten miteinander zu rechnen war.It is surprising that according to the process of the invention using basic organic nitrogen compounds, 2-chloro-5-methylpyridine can be obtained in a considerably higher yield than according to the previously known methodology, since when phosphoryl chloride and basic organic nitrogen compounds are used side by side by-products from the reaction of these components were more likely.
Vorteile des erfindungsgemäßen Verfahrens liegen neben der guten Ausbeute am gewünschten Produkt auch darin, daß der Anteil an isomeren Nebenprodukten wesentlich geringer als bei der bisher bekannten Synthesemethode ist. Weiterhin kann man, falls erwünscht, aus dem Reaktionsprodukt die reine Verbindung (I) leicht durch übliche Methoden, zum Beispiel durch destillative Trennung herstellen.In addition to the good yield of the desired product, advantages of the process according to the invention are also that the proportion of isomeric by-products is significant is lower than in the previously known synthesis method. Furthermore, if desired, the pure compound (I) can easily be prepared from the reaction product by customary methods, for example by separation by distillation.
Das erfindungsgemäße Verfahren stellt somit eine wertvolle Bereicherung der Technik dar.The method according to the invention thus represents a valuable enrichment of the technology.
Der Reaktionsablauf beim erfindungsgemäßen Verfahren kann durch das nachstehende Formelschema skizziert werden:
Die Ausgangsstoffe für das erfindungsgemäße Verfahren - 3-Methyl-pyridin-1-oxid und Phosphorylchlorid - sind bekannt (vgl. J. Am. Chem. Soc. 76 (1954), 1286-1291).The course of the reaction in the process according to the invention can be outlined using the following formula:
The starting materials for the process according to the invention - 3-methyl-pyridine-1-oxide and phosphoryl chloride - are known (cf. J. Am. Chem. Soc. 76 (1954), 1286-1291).
Das erfindungsgemäße Verfahren wird in Gegenwart einer basischen Stickstoffverbindung der Reihe Dialkylamine, wie z. B. Diethylamin, Dipropylamin, Diisopropylamin, Dibutylamin, Diisobutylamin und Di-sec-butylamin, Trialkylamine, wie z. B. Triethylamin, Tripropylamin und Tributylamin, Dialkyl-cycloalkylamine, wie z. B. Dimethyl-cyclopentylamin, Diethyl-cyclopentylamin, Dimethyl-cyclohexylamin und Dietyl-cyclohexylamin, Dialkyl-aralkylamine, wie z. B. Dimethyl-benzylamin und Diethyl-benzylamin sowie Dialkylarylamine, wie z. B. Dimethylanilin, durchgeführt.The inventive method is in the presence of a basic nitrogen compound of the series dialkylamines, such as. As diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine and di-sec-butylamine, trialkylamines, such as. B. triethylamine, tripropylamine and tributylamine, dialkyl-cycloalkylamines, such as. B. dimethyl-cyclopentylamine, diethyl-cyclopentylamine, dimethyl-cyclohexylamine and dietyl-cyclohexylamine, dialkyl-aralkylamines such as e.g. B. dimethyl-benzylamine and diethyl-benzylamine and dialkylarylamines, such as. B. Dimethylaniline performed.
Diisopropylamin wird als basische organische Stickstoffverbindung besonders bevorzugt.Diisopropylamine is particularly preferred as the basic organic nitrogen compound.
Das erfindungsgemäße Verfahren wird in Gegenwart eines inerten organischen Lösungsmittels durchgeführt. Hierzu gehören vorzugsweise gegebenenfalls halogenierte Kohlenwasserstoffe, wie Pentan, Hexan, Heptan, Octan, Cyclohexan, Methylcyclohexan, Petrolether, Benzin, Ligroin, Benzol, Toluol, Xylol, Methylenchlorid, Chloroform, Tetrachlormethan, 1,2-Dichlorethan, Chlorbenzol und Dichlorbenzol, Ether, wie Diethylether, Dipropylether, Diisopropylether, Dibutylether, Methyl- tert-butylether, Glycoldimethylether, Diglycoldimethylether, Tetrahydrofuran und Dioxan, Ketone, wie Aceton, Methylethylketon, Diethylketon, Methyl-isopropylketon und Methyl-isobutylketon, Ester, wie Essigsäuremethylester, Essigsäureethylester, Essigsäurepropylester, Essigsäurebutylester und Essigsäureamylester, Nitrile, wie Acetonitril und Propionitril, Amide wie Dimethylformamid, Dimethylacetamid und N-Methyl-pyrrolidon, sowie Dimethylsulfoxid und Sulfolan.The process according to the invention is carried out in the presence of an inert organic solvent. These preferably include optionally halogenated hydrocarbons, such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene, ether, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone acid, ethyl acetate, such as ethyl acetate, ethyl acetate, such as ethyl acetate, such as ethyl acetate, such as ethyl acetate, such as ethyl acetate, and amyl acetate, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulfoxide and sulfolane.
Methylenchlorid wird als Verdünnungsmittel besonders bevorzugt.Methylene chloride is particularly preferred as a diluent.
Die Reaktionstemperaturen können bei dem erfindungsgemäßen Verfahren in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -50 °C und +50 °C, vorzugsweise bei Temperaturen zwischen -20 °C und +20 °C.The reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between -50 ° C and +50 ° C, preferably at temperatures between -20 ° C and +20 ° C.
Das erfindungsgemäße Verfahren wird im allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch möglich, unter erhöhtem oder vermindertem Druck zwischen 0,1 und 10 bar zu arbeiten.The process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure between 0.1 and 10 bar.
Zur Durchführung des erfindungsgemäßen Verfahrens setzt man auf 1 Mol 3-Methyl-pyridin-1-oxid der Formel (II) im allgemeinen zwischen 1 und 10 Mol, vorzugsweise zwischen 1,5 und 2,5 Mol, Phosphorylchlorid und ebenfalls zwischen 1 und 10 Mol, vorzugsweise zwischen 1,5 und 2,5 Mol, der basischen organischen Stickstoffverbindung ein. Der Einsatz von angenähert je 2 Mol Phosphorylchlorid und Stickstoffverbindung je Mol 3-Methyl-pyridin-1-oxid wird besonders bevorzugt.To carry out the process according to the invention, 1 mol of 3-methyl-pyridine-1-oxide of the formula (II) is generally employed between 1 and 10 mol, preferably between 1.5 and 2.5 mol, phosphoryl chloride and likewise between 1 and 10 Moles, preferably between 1.5 and 2.5 moles, of the basic organic nitrogen compound. The use of approximately 2 moles of phosphoryl chloride and nitrogen compound per mole of 3-methyl-pyridine-1-oxide is particularly preferred.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird das 3-Methyl-pyridin-1-oxid in einem Verdünnungsmittel vorgelegt und unter Rühren und Kühlen das in einem inerten organischen Lösungsmittel gelöste Phosphorylchlorid und die ebenfalls in einem inerten organischen Lösungsmittel gelöste basische organische Stickstoffverbindung gleichzeitig ("simultan", "parallel") eindosiert, wobei vorzugsweise die Zugabe des Phosphorylchlorids mit einem kleinen zeitlichen Vorsprung erfolgt, so daß bereits zwischen 5 % und 20 % des Phosphorylchlorids im Reaktionsgemisch vorliegen, wenn mit der Zugabe der basischen organischen Stickstoffverbindung begonnen wird. Das komplette Reaktionsgemisch wird bis zum Ende der Umsetzung gerührt.In a preferred embodiment of the process according to the invention, the 3-methyl-pyridine-1-oxide is initially introduced into a diluent and, while stirring and cooling, the phosphoryl chloride dissolved in an inert organic solvent and the basic organic nitrogen compound likewise dissolved in an inert organic solvent are simultaneously (" simultaneously "," in parallel "), preferably adding the phosphoryl chloride with a small time advantage, so that between 5% and 20% of the phosphoryl chloride is present in the reaction mixture when the addition of the basic organic nitrogen compound is started. The complete reaction mixture is stirred until the reaction has ended.
Die Aufarbeitung kann auf übliche Weise durchgeführt werden. Vorzugsweise wird das Reaktionsgemisch unter Rühren und Kühlen mit Wasser versetzt, das organische Lösungsmittel - beispielsweise durch Destillation - entfernt, die wäßrige Phase mit einer wäßrigen Alkalimetall- oder Erdalkalimetall-hydroxidlösung, wie z. B. Natronlauge, auf pH 6 eingestellt und das Reaktionsprodukt daraus weitgehend durch Wasserdampfdestillation entfernt. Der organische Anteil des Wasserdampfdestillats enthält im wesentlichen das Produkt der Formel (I).The workup can be carried out in the usual way. Water is preferably added to the reaction mixture with stirring and cooling, the organic solvent is removed, for example by distillation, and the aqueous phase is dissolved in an aqueous alkali metal or alkaline earth metal hydroxide solution, such as, for. B. sodium hydroxide solution, adjusted to pH 6 and the reaction product largely removed by steam distillation. The organic portion of the steam distillate essentially contains the product of formula (I).
Die Reindarstellung der Verbindung der Formel (I) aus dem organischen Anteil des Wasserdampfdestillats kann nach üblichen Methoden, beispielsweise durch eine Feindestillation an einer Füllkörperkolonne erfolgen. Die Verbindung der Formel (I) hat bei einem Druck von 3,3 mb einen Siedepunkt von 56°C. Die Gesamtausbeute bei der Herstellung von reinem Produkt (I) beträgt ausgehend vom 3-Methyl-pyridin-1-oxid 55-62 % der Theorie.The pure preparation of the compound of formula (I) from the organic portion of the steam distillate can be carried out by customary methods, for example by fine distillation on a packed column. The compound of formula (I) has a boiling point of 56 ° C. at a pressure of 3.3 mb. The overall yield in the production of pure product (I) starting from 3-methyl-pyridine-1-oxide is 55-62% of theory.
Das nach dem erfindungsgemäßen Verfahren herstellbare 2-Chlor-5-methyl-pyridin ist als Zwischenprodukt für Pharmazeutika bekannt (vgl. DE-OS 28 12 585).The 2-chloro-5-methyl-pyridine which can be prepared by the process according to the invention is known as an intermediate for pharmaceuticals (cf. DE-OS 28 12 585).
Weiterhin kann 2-Chlor-5-methyl-pyridin als Zwischenprodukt für insektizide Wirkstoffe eingesetzt werden.Furthermore, 2-chloro-5-methyl-pyridine can be used as an intermediate for active insecticides.
Zu 27,3 g (0,25 Mol) 3-Methyl-pyridin-1-oxid in 400 ml Methylenchlorid läßt man bei ca. -10 °C 10 % einer Lösung von 76,7 g (0,5 Mol) Phosphorylchlorid in 50 ml Methylenchlorid zutropfen. Die restlichen 90 % dieser Lösung werden danach simultan mit einer Mischung von 50,6 g (0,5 Mol) Diisopropylamin in 50 ml Methylenchlorid innerhalb von 3 Stunden bei -10 °C zugetropft. Man rührt ca. 2 1/2 Stunden bei dieser Temperatur nach. Anschließend gibt man unter Kühlung 75 ml Wasser hinzu, destilliert das Methylenchlorid ab, stellt die Reaktionsmischung mit ca. 290 ml 20 %iger Natronlauge auf pH 6 und führt eine Wasserdampfdestillation durch.10.3% of a solution of 76.7 g (0.5 mol) of phosphoryl chloride are added to 27.3 g (0.25 mol) of 3-methyl-pyridine-1-oxide in 400 ml of methylene chloride at about -10 ° C. Add 50 ml of methylene chloride dropwise. The remaining 90% of this solution are then added dropwise simultaneously with a mixture of 50.6 g (0.5 mol) of diisopropylamine in 50 ml of methylene chloride at -10 ° C. in the course of 3 hours. The mixture is stirred at this temperature for about 2 1/2 hours. Then, with cooling, 75 ml of water are added, the methylene chloride is distilled off, the reaction mixture is adjusted to pH 6 with about 290 ml of 20% sodium hydroxide solution and steam distillation is carried out.
Nach üblicher Aufarbeitung erhält man 20,5 g eines Produktgemischs, das nach dem Gaschromatogramm (100 % Methode) folgende Zusammensetzung aufweist:
81 % 2-Chlor-5-methylpyridin,
15 % 2-Chlor-3-methylpyridin, und
1 % β-Picolin.After customary working up, 20.5 g of a product mixture are obtained which, according to the gas chromatogram (100% method), has the following composition:
81% 2-chloro-5-methylpyridine,
15% 2-chloro-3-methylpyridine, and
1% β-picoline.
Claims (7)
- Process for the preparation of 2-chloro-5-methyl-pyridine of the formula (I)
- Process according to Claim 1, characterized in that the basic organic nitrogen compound used is diisopropylamine.
- Process according to Claim 1 and 2, characterized in that the inert organic solvent used is methylene chloride.
- Process according to Claim 1-3, characterized in that the reaction is carried out at -20°C to +20°C.
- Process according to Claim 1-4, characterized in that 1 to 10 moles of the basic organic nitrogen compound are used per mole of 3-methylpyridine 1-oxide.
- Process according to Claim 1 to 5, characterized in that the reaction mixture formed in the reaction is subjected to steam distillation.
- Process according to Claim 1 to 6, characterized in that a further separation by distillation is carried out to obtain the pure compound (I).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3800179 | 1988-01-07 | ||
| DE3800179A DE3800179A1 (en) | 1988-01-07 | 1988-01-07 | METHOD FOR PRODUCING 2-CHLORINE-5-METHYL-PYRIDINE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0324174A2 EP0324174A2 (en) | 1989-07-19 |
| EP0324174A3 EP0324174A3 (en) | 1990-05-30 |
| EP0324174B1 true EP0324174B1 (en) | 1993-10-27 |
Family
ID=6344872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88121826A Expired - Lifetime EP0324174B1 (en) | 1988-01-07 | 1988-12-29 | Process for the preparation of 2-chloro-5-methylpyridine |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4897488A (en) |
| EP (1) | EP0324174B1 (en) |
| JP (1) | JP2505557B2 (en) |
| KR (1) | KR970008315B1 (en) |
| DE (2) | DE3800179A1 (en) |
| HU (1) | HU202204B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3839332A1 (en) * | 1988-11-22 | 1990-05-23 | Bayer Ag | METHOD FOR PRODUCING SUBSTITUTED 2-CHLORINE PYRIDINES |
| DE4020053A1 (en) * | 1990-01-31 | 1991-08-01 | Bayer Ag | METHOD FOR PRODUCING 2-CHLORINE-5-METHYL-PYRIDINE |
| DE4020052A1 (en) * | 1990-06-23 | 1992-01-02 | Bayer Ag | METHOD FOR PRODUCING 2-CHLORINE-5-METHYL-PYRIDINE |
| DE4234637A1 (en) * | 1992-10-14 | 1994-04-21 | Bayer Ag | Process for the preparation of 2-substituted 5-alkyl-pyridines |
| US6197962B1 (en) | 1998-01-26 | 2001-03-06 | Kuraray Co., Ltd. | Method for producing 2-sulfonylpyridine derivatives and method for producing 2-{[(2-pyridyl)methyl]thio}-1H-benzimidazole derivatives |
| US6350876B2 (en) | 1998-01-26 | 2002-02-26 | Kuraray Co., Ltd. | 4-chloro-3,5-dimethyl-2-sulfonyl pyridines |
| JP5702595B2 (en) * | 2009-12-25 | 2015-04-15 | 石原産業株式会社 | Process for producing 2-chloro-3-trifluoromethylpyridine |
| MX2015017254A (en) | 2013-06-14 | 2016-12-14 | Cheminova As | A method for producing 2,3-dichloro-5-(trichloromethyl)pyridine. |
| CN106660956A (en) * | 2014-01-27 | 2017-05-10 | 弗特鲁斯控股有限责任公司 | Process for making 2-chloro-5-methylpyridine |
-
1988
- 1988-01-07 DE DE3800179A patent/DE3800179A1/en not_active Withdrawn
- 1988-12-27 JP JP63328080A patent/JP2505557B2/en not_active Expired - Fee Related
- 1988-12-29 DE DE88121826T patent/DE3885262D1/en not_active Expired - Fee Related
- 1988-12-29 EP EP88121826A patent/EP0324174B1/en not_active Expired - Lifetime
-
1989
- 1989-01-04 US US07/293,260 patent/US4897488A/en not_active Expired - Lifetime
- 1989-01-04 HU HU8923A patent/HU202204B/en not_active IP Right Cessation
- 1989-01-06 KR KR1019890000060A patent/KR970008315B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2505557B2 (en) | 1996-06-12 |
| DE3885262D1 (en) | 1993-12-02 |
| EP0324174A3 (en) | 1990-05-30 |
| DE3800179A1 (en) | 1989-07-20 |
| EP0324174A2 (en) | 1989-07-19 |
| JPH01213263A (en) | 1989-08-28 |
| US4897488A (en) | 1990-01-30 |
| HU202204B (en) | 1991-02-28 |
| KR890011846A (en) | 1989-08-22 |
| KR970008315B1 (en) | 1997-05-23 |
| HUT50124A (en) | 1989-12-28 |
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